화학공학소재연구정보센터
Journal of Chemical Physics, Vol.107, No.12, 4537-4545, 1997
H+N2O collision dynamics: Branching ratios for T-V energy transfer and the effect of N2O vibrational excitation on the reaction kinetics
We report time-resolved Fourier transform spectroscopic measurements on the kinetics of the reaction of vibrationally excited N2O with hydrogen atoms. Vibrationally excited N2O is formed by T-V energy transfer in collisions with hydrogen atoms having 2.3 eV of translational energy. Although the T-V process is capable of exciting the N2O to vibrational levels up to 18500 cm(-1), collisions in which the relative translational energy is greater than 11000 cm(-1) result in rapid reaction to form either NH(X (3) Sigma) + NO(X (II)-I-2) or OH(A (2) Sigma(+)) + N-2(X (1) Sigma(+)). N2O which is vibrationally excited to energies between 6000 and 11000 cm(-1), reacts with thermal hydrogen atoms, with a rate constant which is about 1.7 X 10(-10) cm(-3) molecule(-1) s(-1). N2O vibrationally excited to levels below 6000 cm(-1) [the height of the barrier to reaction forming OH(X (II)-I-2) + N-2 on the ground-state surface] is lost very slowly, presumably by deactivation, with a rate constant which is about four orders of magnitude slower than the reaction. The results indicate that increasing the vibrational energy of the N2O by 11000 cm(-1) increases the cross section for the reaction with hydrogen atoms by about seven orders of magnitude. (C) 1997 American Institute of Physics.